Methods for removing a contaminant by a polyoxometalate-modified fabric or a polyoxometalate-modified cellulosic fiber and fabrics thereof

ABSTRACT

The invention relates to a method for removing a contaminant from a gas phase or a liquid phase by contacting an article composed of (1) a fabric or cellulosic fiber and (2) a polyoxometalate, wherein the polyoxometalate is incorporated in the fabric or cellulosic fiber, with the gas phase or liquid phase containing the contaminant. The invention further relates to a polyoxometalate-modified fabric composed of a fabric and a polyoxometalate of the present invention incorporated in the fabric. The invention further relates to an article containing the polyoxometalate-modified fabric. The invention further relates to a method for making the polyoxometalate-modified fabric, by contacting the fabric with a polyoxometalate to produce a polyoxometalate-modified fabric.

FIELD OF THE INVENTION

[0001] The present invention relates to methods for removing acontaminant by a polyoxometalate-modified fabric or apolyoxometalate-modified cellulosic fiber from the gas or liquid phase.The invention further relates to polyoxometalate-modified fabrics andarticles comprising a polyoxometalate-modified fabric.

BACKGROUND OF THE INVENTION

[0002] Decreasing the potential danger of toxic gases has long been asignificant issue. Offensive odors originating from cigarette smoke,sweat, exhaust gases, and rotten food in the work place, the home, andelsewhere are caused by thousands of gaseous components. Examples ofdeleterious and/or foul-smelling compounds include, but are not limitedto, acetaldehyde, hydrogen sulfide, methyl mercaptan, ammonia,trimethylamine, and nicotine.

[0003] The goal is to fabricate and-use self-deodorizing fabrics andcellulosic fibers in the form of clothing, furniture upholstery,curtains, carpets, or paper to remove or degrade gaseous or liquid toxicand/or malodorous compounds in the work place and home. Textilesproduced in Japan are known to remove contaminants from the gas phase.Some of the Japanese textiles have carbonate anions or aminesincorporated within the fiber. CLEAN GUARD, which is manufactured byKomatsu Seiren Co., LTD of Japan, contains finely divided ceramics andamphoteric oxides as the deodorizing components incorporated within thefabric. Smoklin®, which is a cloth composed of polyacrylic yarnmanufactured by Asahi Chemical Industry Company, can also removecontaminants from the gas phase. U.S. Pat. No. 5,603,927 to Fukumoto etal. discloses the incorporation of acid salts of aniline halides, aminobenzoic acid, sulfanilamide or derivatives thereof, or aminoacetophenoneinto a porous carrier such as a fiber or cloth in order to removeoffensive odors.

[0004] The prior art in this area, however, demonstrates a seriousshortcoming, namely that the materials are effective only throughstoichiometric physisorption or chemisorption processes based onacid-base, ion pairing (salt formation) and/or oxidation-reductionreactions. Because this technology is stoichiometric and not catalytic,it is not very practical and economical.

[0005] The incorporation of a polyoxometalate (herein referred to as“POM”) into a fabric or cellulosic fiber in order to remove acontaminant from the gas phase has not been disclosed in the art.Furthermore, the prior art is very limited with respect to the use of apolyoxometalate-modified fabric or cellulosic fiber for the removal of acontaminant from the liquid phase. Gall et al. (Chem. Mat. 8, pp.2523-2527, 1996) disclose the immobilization of H₅PV₂Mo₁₀O₄₀ on carboncloth in order to determine the ability of H₅PV₂Mo₁₀O₄₀ to remove sulfurcontaining compounds from toluene. However, Gall et al. did notinvestigate the removal of sulfur containing compounds from the gasphase.

[0006] Typically, heteropoly and isopoly acids, which are subsets ofpolyoxometalates, are used as pigments and dyes when they areincorporated into a fabric. Japanese Patent Application No. JP 50136488to Kakinuma et al. discloses contacting yarn with a heteropoly acid ortartaric acid to improve the lightfastness of the yarn. Japanese PatentNo. JP 82014477 B discloses the lightfastness of yarn is improved whenthe yarn is contacted with an aqueous solution of phosphomolybdic acid.

[0007] JP 5179188, JP 61185568, and JP 62013464 disclose that heteropolyacids such as phosphotungstic acid, phosphomolybdic acid, silicomolybdicacid, silicotungstic acid, phosphotungstomolybdic acid,phosphovanadomolybdic acid, and their salts can be used as colorants andpigments for ink compositions. U.S. Pat. No. 3,947,332 to Vanderpool etal. disclose the synthesis of heteropoly acids containing tungsten ormolybdenum and at least one other element having a positive valence from2 to 7. The heteropoly acids disclosed in Vanderpool et al. can be usedin printing inks and paper coloring.

[0008] U.S. Pat. No. 3,925,006 to Forschirm et al. discloses firstcontacting a cellulose ester with sodium tungstophosphate or sodiumtungstosilicate followed by contacting the cellulose ester with acationic dye. The sodium tungstophosphate and sodium tungstosilicateimprove the uptake of the cationic dye into the cellulose ester. U.S.Pat. No. 4,444,592 to Ludwig discloses the preparation of a pigment thatis the reaction product between a heteropoly acid and pararosaniline.The water insoluble pigment can be used in the textile arts. Chem. Rev.1998, 98, pp. 359-387 to Katsoulis is a comprehensive review articlethat discloses the use of POMs as dyes and pigments.

[0009] Japanese-Patent No. JP. 71036516 B discloses a method forresin-ireating textile goods containing cellulosic or hydrophobicfibers. The cellulosic fiber is treated with an isopoly or heteropolyacid. The resultant cellulosic fiber possesses increased soil-and-creaseresistance and wash-and-wear properties. International PatentApplication No. 94/20565 to Jackson et al. discloses contacting anaramid with an aqueous solution of a tungsten compound, preferablyphosphotungstic acid and ammonium metatungstate, in order to decreasethe flammability of textile articles. None of the references describedabove disclose the removal of a contaminant from the gas or liquidphase.

[0010] A POM-based fixed-bed catalytic reactor for the purification ofgas in vents or passages has been disclosed in Japanese PatentApplication No. 0435716 to Aido et al. This reactor involves a POM(H₃PMo₆W₆O₄₀) immobilized on a porous moulding of cordierite.

[0011] Japanese Patent Application No. 7251075 discloses the gas phaseoxidation of unsaturated aldehydes to the corresponding carboxylic acidby a heteropoly acid catalyst containing molybdenum and vanadium. Thecatalyst is used in combination with carbon fibers. There is nodisclosure in JP 7251075, however, for the removal of a contaminant fromthe gas or liquid phase.

[0012] In light of the above, it would be very desirable to have anarticle and a method of using an article for the removal of toxic and/ormalodorous compounds without adding stoichiometric amounts of additivesor compounds to the article. The present invention solves such a need inthe art while providing surprising advantages. The present inventionherein incorporates a catalytically active early-transition-metal oxygenanion cluster (polyoxometalate or POM) into textiles, fabrics, andcellulosic fibers, including the Japanese deodorizing fabrics describedabove, which greatly increases the ability of the fabric to removetoxic, offensive and/or odorous compounds from the gas and liquid phase.

SUMMARY OF THE INVENTION

[0013] In accordance with the purpose(s) of this invention, as embodiedand broadly described herein, this invention, in one aspect; relates toa method for removing a contaminant from the gas phase, comprisingcontacting an article comprising a fabric and at least onepolyoxometalate, wherein the polyoxometalate is incorporated in thefabric to produce a polyoxometalate-modified fabric, with the gas phasecontaining the contaminant.

[0014] The invention further relates to a method for removing acontaminant from the liquid phase, comprising contacting an articlecomprising a fabric and at least one polyoxometalate, wherein thepolyoxometalate is incorporated in the fabric to produce apolyoxometalate-modified fabric, with the liquid phase containing thecontaminant, with the proviso that when the fabric is carbon cloth, thenthe polyoxometalate is not H₅PV₂Mo₁₀O₄₀.

[0015] The invention further relates to a method for removing acontaminant from the gas phase or liquid phase, comprising contacting anarticle comprising a cellulosic fiber and at least one polyoxometalate,wherein the polyoxometalate is incorporated in the cellulosic fiber toproduce a polyoxometalate-modified cellulosic fiber, with the gas phaseor liquid phase containing the contaminant.

[0016] The invention further relates to a polyoxometalate-modifiedfabric, comprising a fabric and at least one polyoxometalate, whereinthe polyoxometalate has the formula[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o, and p is greater than or equal tofour; and the sum of k, m, and q is greater than zero, and A is acounterion, wherein the polyoxometalate is incorporated in the fabric,

[0017] with the proviso that when A is a proton, the polyoxometalate isnot the reaction product between[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A] and apararosaniline compound,

[0018] with the further proviso that the polyoxometalate is notsilicomolybdenic acid or its sodium salt, phosphomolybdenic acid,ammonium chromododecanemolybdenate, ammonium salt of hydrogenhexamolybdocobaltic acid, para-tungstic acid or its ammonium salt orsodium salt, meta-tungstic acid or its ammonium salt or sodium salt,phosphotungstic acid or its salt, silicotungstic acid or its salt,dodecane tungstodicobaltic acid or its salt, phosphotungstomolybdenicacid or its salt, or phosphovanadomolybdenic acid or its salt,

[0019] with the further proviso that when the fabric is carbon cloth,the polyoxometalate is not H₅PV₂Mo₁₀O₄₀.

[0020] The invention further relates to an article comprising apolyoxometalate-modified fabric.

[0021] The invention further relates to a method of making apolyoxometalate-modified fabric comprising contacting the fabric withthe polyoxometalate to produce the polyoxometalate-modified fabric.

[0022] Additional advantages of the invention will be set forth in partin the description which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations. It is to be understood that both theforegoing general description and the following detailed description areexemplary and explanatory only and are not restrictive of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023]FIG. 1 shows the DRIFT spectra of 1-acrylic (5 wt % of 1, bottom)and unsupported 1 powder (top), where 1 is H₅PV₂Mo₁₀O₄₀.

[0024]FIG. 2 shows the SEM pictures of acrylic (top) and 1-acrylic (5 wt% of 1, bottom).

[0025]FIG. 3 shows the aerobic oxidation of gaseous CH₃CHO by Smoklin®and Smoklin® with adsorbed 1.

DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention may be understood more readily by referenceto the following detailed description of preferred embodiments of theinvention and the Examples included therein.

[0027] Before the present methods and articles are disclosed anddescribed, it is to be understood that this invention is not limited tospecific synthetic methods or to particular formulations, as such may,of course, vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only andis not intended to be limiting.

[0028] In this specification and in the claims which follow, referencewill be made to a number of terms which shall be defined to have thefollowing meanings:

[0029] The singular forms “a,” “an” and “the” include plural referentsunless the context clearly dictates otherwise.

[0030] “Optional” or “optionally” means that the subsequently describedevent or circumstance may or may not occur, and that the descriptionincludes instances where said event or circumstance occurs and instanceswhere it does not.

[0031] In accordance with the purpose(s) of this invention, as embodiedand broadly described herein, this invention, in one aspect, relates toa method for removing a contaminant from the gas phase, comprisingcontacting an article comprising a fabric and at least onepolyoxometalate, wherein the polyoxometalate is incorporated in thefabric to produce a polyoxometalate-modified fabric, with the gas phasecontaining the contaminant.

[0032] The invention further relates to a method for removing acontaminant from the liquid phase, comprising contacting an articlecomprising a fabric and at least one polyoxometalate, wherein thepolyoxometalate is incorporated in the fabric to produce apolyoxometalate-modified fabric, with the liquid phase containing thecontaminant, with the proviso that when the fabric is carbon cloth, thenthe polyoxometalate is not H₅PV₂Mo₁₀O₄₀.

[0033] The invention further relates to a method for removing acontaminant from the gas phase or liquid phase, comprising contacting anarticle comprising a cellulosic fiber and at least one polyoxometalate,wherein the polyoxometalate is incorporated in the cellulosic fiber toproduce a polyoxometalate-modified cellulosic fiber, with the gas phaseor liquid phase containing the contaminant.

[0034] Many polyoxometalates known in the art can be used in the presentinvention to remove a contaminant from the gas phase. Polyoxometalatesare also referred to in the art as heteropoly compounds, heteropolyacids, isopoly compounds, and isopoly acids, which are subsets ofpolyoxometalates. Examples of polyoxometalates useful in the presentinvention are disclosed in Pope, M. T. in Heteropoly and IsopolyOxometalates, Springer Verlag, 1983, and Chemical Reviews, vol. 98, no.1, pp. 1-389, 1998, which are incorporated by this reference in theirentirety.

[0035] The selection of the polyoxometalate used in the presentinvention is dependent upon the contaminant or contaminants to beremoved from the gas phase or liquid phase. In one embodiment, thepolyoxometalate has the formula[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o, and p is greater than or equal tofour; and the sum of k, m, and q is greater than zero, and A is acounterion. In one embodiment, s is from 19 to 460. The charge on thePOM, y, is dictated by the values of k, m, n, o, p, q, r and s. The p-,d-, and f-bock elements can exist in any oxidation state.

[0036] The counterion A can be any counterion known in the art. Examplesof counterions include, but are not limited to, quatemary ammoniumcation, proton, alkali metal cation, alkaline earth metal cation,ammonium cation, d-block cations, f-block cations, or a combinationthereof. In one embodiment, the polyoxometalate is an acid, wherein thecounterion A is H⁺. In one embodiment, the counterion is a d- or f-blockmetal complex. In one embodiment, the counterion istrimethyl-triazacyclononane manganese. In another embodiment, thecounterion is silver or gold. Not wishing to be bound by theory, it isbelieved that some counterions of the present invention can be reducedto the corresponding metal when the polyoxometalate contacts thecontaminant. For example, when the cation is Ag⁺¹ or Au⁺¹, these cationscan be reduced to silver metal or gold metal, respectively, dependingupon the contaminant that is to be removed.

[0037] Generally, M can be any d-block element having at least oned-electron. Typically, M comprises titanium, chromium, manganese,cobalt, iron, nickel, copper, rhodium, silver, palladium, platinum,mercury, or ruthenium. In a preferred embodiment, M comprises manganese,cobalt, or ruthenium. In another embodiment, X comprises phosphorus,silicon, aluminum, boron, cobalt, zinc, or iron. When thepolyoxometalate has the Keggin structure XM₁₂, then it is possible for Xand at least one M to be the same d- or f-block element. Not wishing tobe bound by theory, it is believed that the metal ion M of thepolyoxometalate of the present invention is responsible for removing thecontaminant from the gas phase, while X, when present, providesstructural integrity to the polyoxometalate.

[0038] In one embodiment, the sum of k and q is greater than or equal toone, the sum of k, m, n, o, p, and q is 12, and s is 40. In yet anotherembodiment, k is not zero. In another embodiment, q is not zero. In apreferred embodiment, the polyoxometalate comprises H₅PV₂Mo₁₀O₄₀,H₄PVMo₁₁O₄₀, H₆PV₃Mo₉O₄₀, Na₉PV₆Mo₆O₄₀, Na₅H₂PV₄Mo₈O₄₀, or K₈Co₂W₁₁O₃₉.

[0039] In another embodiment, the polyoxometalate has the formula[X^(g+)V_(b)M^(h+) _(c)Z_(12-b-c)O₄₀]^(u−)[A], wherein X is at least onep-, d-, or f-block element; g+ is the charge of X; M is at least onef-block element or d-block element having at least one d-electron,wherein M is not vanadium; h+ is the charge of M; Z is tungsten,molybdenum, niobium, or a combination thereof; b is from 0 to 6; c isfrom 0 to 6, wherein the sum of b and c is greater than or equal to one;u is greater than 3; and A is a counterion.

[0040] In another embodiment, the polyoxometalate has the formula[X^(g+)V_(b)Z_(12-b)O₄₀]^(u−)[A], wherein X is at least one phosphorus,silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten,molybdenum, niobium, or a combination thereof; b is from 1 to 6; and uis greater than 3.

[0041] In another embodiment, the polyoxometalate has the structure[X^(g+M) ^(h+) _(c)Z_(12-c)O₄₀]^(u−)[A], wherein X is at least onephosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprisestungsten, molybdenum, niobium, or a combination thereof; M^(h+) is atleast one f-block element or d-block element having at least oned-electron; c is from 1 to 6; and u is greater than 3.

[0042] In another embodiment, the polyoxometalate has the formula[X^(i+) ₂V_(u)M^(j+)Z_(18-u-v)O₆₂]^(w−)[A], wherein X is at least onep-, d-, or f-block element i+ is the charge of X; M is at least one d-or f-block element, wherein M is not vanadium; j+ is the charge of M; Zis tungsten, molybdenum, niobium, or a combination thereof; u is from 0to 9; y is from 0 to 9, wherein the sum of u and v is greater than orequal to one; w is greater than or equal to 4; and A is a counterion.

[0043] In another embodiment, the polyoxometalate has the formula[X^(i+) ₂V_(u)Z_(18-u)O₆₂]^(w−)[A], wherein X is at least onephosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Zcomprises tungsten, molybdenum, niobium, or a combination thereof; u isfrom 1 to 9; and w is greater than or equal to 4.

[0044] In another embodiment, the polyoxometalate has the formula[X^(i+) ₂M^(j+) _(v)Z_(18-v)O₆₂]^(w−)[A], wherein X is at least onephosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Zcomprises tungsten, molybdenum, niobium, or a combination thereof;M^(j+) is at least one d- or f-block element; v is from 1 to 9; and w isgreater than or equal to 4.

[0045] In another embodiment, the polyoxometalate has the formula[YV_(x)Z_(12-x)O₄₀][A], wherein Y is phosphorus, silicon, or aluminum; Zis tungsten or molybdenum; x is from 1 to 6, and A is a counterion. Inone embodiment, Y is phosphorus and Z is molybdenum. In one embodiment,Y is phosphorus and Z is tungsten. In one embodiment, Y is silicon and Zis molybdenum. In one embodiment, Y is silicon and Z is tungsten. In oneembodiment, Y is aluminum and Z is tungsten. In one embodiment, Y isaluminum and Z is molybdenum.

[0046] Polyoxometalates having an organic group, such as an alkyl groupor aryl group, an organosilyl group, or other p- or d-blockorganometallic groups bonded to the POM can also be used in the presentinvention. The organic group can be branched or straight chain alkyl,alkenyl, or allynyl group or an aryl group of C₁ to C₃₀. The alkyl groupcan also be a polyether or polyol. Not wishing to be bound by theory,the organic group is bonded to the polyoxometalate as depicted in Scheme1, where R is the organic group:

[0047] The reaction between an alcohol and the polyoxometalate I resultsin the loss of water and the formation of the polyoxometalate II,wherein the organic group is bonded to an oxygen atom of thepolyoxometalate. Any alcohol known in the art can be used in the presentinvention. Examples of alcohols that can be used include, but are notlimited, to, methanol, ethanol, or tris(hydroxymethyl)methane. Thepolyoxometalates having organic groups bonded to the POM that aredisclosed in Gouzerh et al., Chem. Rev., 98, pp. 77-111, 1998, which isincorporated by reference in its entirety, are useful in the presentinvention.

[0048] In another embodiment, the polyoxometalate I can be reacted witha compound having the generic formula YA_(o)R_(4-o), wherein Y issilicon, tin, or an other p- or d-block element; A is a leaving group; Ris an organic group, such as an alkyl, alkenyl, or alkynyl group or anaryl group of C₁ to C₃₀; and o is from 1 to 4. Suitable leaving groupsfor A include, but are not limited to, halides and alkoxides. In SchemeI, the oxygen of polyoxometalate I displaces A from YAR₃ to form a newY—O bond (compound III). Any silyl, tin, or organic derivative of a p-or d-block element known in the art can be used in the presentinvention, provided that the compound has at least one leaving group.Typically, Met in Scheme I is vanadium, molybdenum, tungsten, niobium,or tantalum.

[0049] A POM of the present invention can be incorporated into anyfabric known in the art to produce a polyoxometalate-modified fabric ofthe present invention. In one embodiment, fabrics used to preparegarments, draperies, carpets, and upholstery can be used and articlesmade from them are a part of this invention. In another embodiment, thefabric can be a knit or non-woven fabric. Fibers useful in preparing thepolyoxometalate-modified fabrics include, but are not limited to,polyamide, cotton, polyacrylic, polyacrylonitrile, polyester,polyvinylidine, polyolefin, polyurethane, polytetrafluoroethylene, orcarbon cloth, or a combination thereof. In one embodiment, the fabric isprepared from cotton, polyacrylic, or polyacrylonitrile. In oneembodiment, the fabric is prepared from a cationic fiber. In anotherembodiment, the fabric comprises (1) a 50/50 blend of nylon-6,6 andcotton or (2) stretchable carbon blended with polyurethane.

[0050] Any cellulosic fiber can be incorporated by a POM to produce apolyoxometalate-modified cellulosic fiber of the present invention.Examples of useful cellulosic fibers include, but are not limited to,wood or paper. In a preferred embodiment, a polyoxometalate of thepresent invention can be incorporated in paper in order to remove acontaminant from the gas or liquid phase. In one embodiment, the paperis wallpaper.

[0051] The amount of polyoxometalate incorporated in the fabric andcellulosic fiber also varies depending upon the contaminant to beremoved. There is no restriction on the amount of POM that can beincorporated into the fabric or cellulosic fiber. In one embodiment, theamount of polyoxometalate incorporated in the fabric is from 2.5 to 60%,2.5 to 35%, 2.5 to 30%, 2.5 to 25%, 2.5 to 20%, and 2.5 to 15% based onweight of the polyoxometalate-modified fabric or cellulosic fiber.

[0052] In one embodiment, the polyoxometalate is H₅PV₂Mo₁₀O₄₀ and thefabric is prepared from a polyacrylic fiber. In another embodiment, thepolyoxometalate is H₅PV₂Mo₁₀O₄₀ and the fabric is prepared from cotton.

[0053] In one embodiment, the polyoxometalate is H₅PV₂Mo₁₀O₄₀ and thecellulosic fiber is paper.

[0054] The present invention is capable of removing a single contaminantor multiple contaminants from the gas or liquid phase. The term “remove”refers to, but is not limited to, the degradation of the contaminant,the conversion of the contaminant into another compound that is eitherless toxic or nontoxic and/or malodorous, or the adsorption of thecontaminant by the polyoxometalate. The POM can degrade the contaminantby a number of different mechanisms. For example, the POM canaerobically oxidize the contaminant acetaldehyde (CH₃CHO). Not wishingto be bound by theory, it is believed that the aerobic oxidation ofCH₃CHO proceeds by a radical chain mechanism (i.e., the initiation ofthe radical chain by CH₃CHO+POM_(OX)−>CH₃CO⁻+HPOM_(red)).

[0055] Containinants that can be removed by using the present inventioninclude, but are not limited to, aliphatic nitrogen compounds such asamines and ammonia; sulfur-containing compounds such as hydrogensulfide, thiols, thiophenes, and thioethers; halogenated compounds; andaliphatic oxygenated compounds, such as aldehydes, ketones, organicacids, and alcohols. In one embodiment, the contarninant isacetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methylsulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine, styrene,propionic acid, n-butyric acid, n-valeric acid, iso-valeric acid, or acombination thereof. In another embodiment, the polyoxometalate-modifiedfabrics and cellulosic fibers can remove mircobial life from the gas orliquid phase. Examples of microbial life include, but are not limitedto, bacteria and protozoa.

[0056] The present invention can remove a contaminant from the gas phaseunder mild conditions. In one embodiment, the contaminant can be removedat from −50° C. to 105° C. at a pressure of from 0.1 to 30 atm,preferably from 25° C. to 105° C. at 1 atm. In a preferred embodiment,the present invention can remove a contaminant from the gas phase atroom temperature (approximately 25° C.) and at 1 atm. These conditionsare very mild when compared to industrial catalysts, which require muchhigher reaction temperatures and pressures in order to promote catalyticactivity. In another embodiment, the present invention can remove acontaminant from the gas phase that has a partial pressure of from 0.1ppb to 2 atm, 10 ppb to 2 atm, 100 ppb to 2 atm, 200 ppb to 0.2 atm, and0.5 ppm to 2 atm. Similarly, the present invention can remove acontaminant from the liquid phase under mild conditions. In oneembodiment, the contaminant can be removed from a liquid media at from0° C. to 200° C. The temperature depends upon the liquid media that isbeing contacted and the contaminant to be removed.

[0057] The gas or liquid phase containing the contaminant can becontacted by the polyoxometalate-modified fabric or cellulosic fiberusing a variety of techniques. For example, when the contaminant is inthe liquid phase, the polyoxometalate-modified fabric or cellulosicfiber can be dipped or submersed into the liquid phase. Alternatively,the liquid phase can be filtered or passed through thepolyoxometalate-modified fabric or cellulosic fiber. When thecontaminant is in the gas phase, the polyoxometalate-modified fabric orcellulosic fiber is typically placed in an open or closed environmentthat contains the contaminant(s).

[0058] The POM modified fabrics and cellulosic fibers of the presentinvention have a number of advantages over the prior art fabrics andfibers that do not use a polyoxometalate to remove a contaminant fromthe gas or liquid phase. One advantage is that the POM modified fabricsand cellulosic fibers are significantly more effective in deodorizationwhen compared to a fabric or fiber that is not modified with a POM ofthe present invention. Another advantage is that the present inventioncan remove a contaminant from the gas or liquid phase starting withinmilliseconds of contact and can remove the contaminant for extendedperiods of time, such as several days or longer. The POMs used in thepresent invention are capable of being regenerated to an active formthat permits the removal of the contaminant. Another advantage is thatsome POMs can render the fabric or cellulosic fiber more water resistantand increase the surface area of the fabric or fiber. Finally, the POMcan enhance the dyeability, light fastness, color fastness, and weavingproperties of the fabric or cellulosic fiber.

[0059] The invention further relates to a polyoxometalate-modifiedfabric, comprising a fabric and at least one polyoxometalate, whereinthe polyoxometalate has the formula[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o and p is greater than or equal tofour, and the sum of k, m, and q is greater than zero, and A is acounterion, wherein the polyoxometalate is incorporated in the fabric,

[0060] with the proviso that when A is a proton, the polyoxometalate isnot the reaction product between[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A] and apararosaniline compound,

[0061] with the further proviso that the polyoxometalate is notsilicomolybdenic acid or its sodium salt, phosphomolybdenic acid,ammonium chromododecanemolybdenate, ammonium salt of hydrogenhexamolybdocobaltic acid, para-tungstic acid or its ammonium salt orsodium salt, meta-tungstic acid or its ammonium salt or sodium salt,phosphotungstic acid or its salt, silicotungstic acid or its salt,dodecane tungstodicobaltic acid or its salt, phosphotungstomolybdenicacid or its salt, or phosphovanadomolybdenic acid or its salt,

[0062] with the further proviso that when the fabric is carbon cloth,the polyoxometalate is not H₅PV₂Mo₁₀O₄₀.

[0063] In one embodiment, k is greater than or equal to one.

[0064] A pararosaniline compound is a compound having the structure IV

[0065] wherein R¹ is hydrogen or methyl and each R² is, independently,hydrogen or substituted or unsubstituted aryl. Examples ofpararosaniline compounds not used in the present invention are disclosedin U.S. Pat. No. 4,444,592 to Ludwig, which is herein incorporated byreference in its entirety.

[0066] The invention further relates to an article comprising apolyoxometalate-modified fabric.

[0067] The invention further relates to a method of making apolyoxometalate-modified fabric, comprising contacting a fabric with apolyoxometalate to produce the polyoxometalate-modified fabric.

[0068] The polyoxometalate can be incorporated into the fabric orcellulosic fiber using techniques known in the art. Examples oftechniques that can be used for incorporating the POM into a fabric orcellulosic fiber include, but are not limited to, depositing the POM onthe surface of an existing fabric or cellulosic fiber, covalentlybonding the POM to the fibers of the fabric or cellulosic fiber,impregnating or intimately mixing the POM with the fabric or cellulosicfiber, electrostatically bonding the POM to the fabric or cellulosicfiber, or datively bonding the POM to the fabric or cellulosic fiber viathe coordination of a d- or f-block metal ion on the surface of the POMwith a functional group on the fabric. In the case of electrostaticallybonding the POM to the fabric or cellulosic fiber, the positivelycharged functional groups on the fabric or cellulosic fiber and thenegatively charged POM can form an electrostatic bond. In oneembodiment, when the counterion of the polyoxometalate is a proton, thefabric or cellulosic fiber can be protonated by the polyoxometalate toproduce a positively charged fiber, which then electrostatically bondsto the polyoxometalate anion. In one embodiment, a cationic polymer canbe used as a binding agent to incorporate an anionic polyoxometalateinto an anionic fiber.

[0069] The polyoxometalates of the present invention can be incorporatedin the fabric and the cellulosic fiber using a variety of techniquesknown in the art. In one embodiment, the fabric or cellulosic fiber iscontacted with a mixture comprising the polyoxometalate and a solvent.The polyoxometalate can be soluble, partially soluble, or insoluble inthe solvent, depending upon the polyoxometalate and solvent selected. Inone embodiment, the solvent is water. In another embodiment, the solventcan be an organic solvent. Examples of organic solvents useful in thepresent invention include, but are not limited to, acetonitrile,acetone, toluene, carbon dioxide, xylenes, 1-methyl-2-pyrrolidinone,dimethyl sulfoxide, or an alcohol, such as methanol, ethanol,1-propanol, or 2-propanol. In another embodiment, the solvent can beused in supercritical drying technology known in the art, which resultsin a finely-divided, high surface-area deposited polyoxometalate on thefabric or cellulosic fiber.

[0070] In one embodiment, the mixture is from 0.1 to 20% by weightpolyoxometalate and from 80 to 99.9% by weight water, preferably from0.3 to 15% by weight polyoxometalate and 85 to 99.7% water. Generally,the fabric or cellulosic fiber is dipped or immersed into the mixturecontaining the POM for several hours to days at a temperature of from 0°C. to 100° C., preferably for 2 hours to 2 days at from 25° C. to 80° C.In another embodiment, the POM can be admixed with a resin or adhesive,and the resultant adhesive is applied to the surface of or admixed withthe fabric or cellulosic fiber.

[0071] Typically, once the fabric or cellulosic fiber has been contactedwith the POM, the polyoxometalate-modified fabric or cellulosic fiber isdried in order to remove residuail solvent. In one embodiment, thepolyoxometalate-modified fabric or cellulosic fiber is heated from 0° C.to 220° C. at or below atmospheric pressure, preferably from 25° C. to100° C. In another embodiment, the polyoxometalate-modified fabric orcellulosic fiber is dried in vacuo (i.e., less than or equal to 10torr). In yet another embodiment, the polyoxometalate-modified fabric orcellulosic fiber is dried under supercritical conditions.

EXAMPLES

[0072] The following examples are put forth so as to provide those ofordinary skill in the art with a complete disclosure and description ofhow the methods and products claimed herein are made and evaluated, andare intended to be purely exemplary of the invention and are notintended to limit the scope of what the inventors regard as theirinvention. Efforts have been made to ensure accuracy with respect tonumbers (e.g., amounts, temperature, etc.) but some errors anddeviations should be accounted for. Unless indicated otherwise, partsare parts by weight, target odorants/toxics are expressed in parts permillion, temperature is in ° C. or is at ambient temperature andpressure is at or near atmospheric.

[0073] The term “consumption” refers to the removal or adsorption of acontaminant or contaminants from the gas phase or the conversion of thecontaminant or contaminants to another compound(s) that is less toxic ornontoxic and/or is less malodorous or not malodorous.

General Considerations

[0074] Materials. The polyoxometalate H₅PV₂Mo₁₀O₄₀ (1), H₄PVMo₁₁O₄₀ (2),and H₆PV₃Mo₉O₄₀ (3) were synthesized and purified following theprocedure disclosed in Pettersson et al., Inorg. Chem. 1994, 33, pp.982, and Tsigdinos et al., Inorg. Chem., 1968, 7, pp. 437-441. ⁵¹V and³¹P NMR were used to check the purity. The samples of Smoklin® (thebrand name of a cloth manufactured by Asahi Chemical Industry Company,Japan, made mainly from polyacrylic yarn), acid-dyeable polyacrylicfiber and the “deep-dye” nylon fiber with NH₂ groups on the polymer endswere tested. The samples of cotton cloth were cut from a common 100%cotton T shirt after laundering. The samples of paper were obtained fromFisher Scientific. All samples were submitted to vacuum and then heated,or washed and then submitted to vacuum and then heated before use. Allsolvents used were purchased from Fisher or Burdick & Jackson companyand had purities of greater than 99%. Acetaldehyde was obtained fromAldrich and exhibited purities greater than 99.9%. Argon, helium, andoxygen were ordered from Specialty Gases (greater than 99.5%). The gasesethane (Matheson), methyl mercaptan (Matheson) and ammonia (AirProducts) were all of greater than 99% purity. All chemicals purchasedwere used as received, except acetaldehyde which was protected under Arin the freezer to minimize adventitious autoxidation (radical chainoxidation by O₂) or other possible reactions.

[0075] Instrumentation. All reactions involving CH₃CHO and CH₃SH weremonitored using a Hewlett-Packard 5890 gas chromatograph equipped withflame ionization detectors and a HP-PLOT Q divinyl-benzene/styreneporous polymer capillary column. The consumption of NH₃ was detected bySensidyne®/Gastec detector tube systems. ⁵¹V NMR measurements werecarried out on a 500-MHZ General Electric GN500 Spectrometer. ³¹P NMRmeasurements were carried out on a 400-MHZ Varian Inova 400Spectrometer. The diffuse reflectance infrared fourier transformspectroscopy (DRIFT measurements for powdered H₅PV₂Mo₁₀O₄₀ and fabricsystems were conducted using a Nicolet 510 FT-IR spectrometer. Thescanning electron microscopy (SEM) experiments were carried out on aISIDS-130/LaB₆EM. Elemental analysis were provided by E+RMicroanalytical Laboratory, Inc.

[0076] Preparation of Fabrics with Supported H₅PV₂Mo₁₀O₄₀ (1).1-Smoklin® cloth and 1-cotton cloth were prepared as follows: a 2-gsample of cloth was immersed in various aqueous solutions of 1 at roomtemperature. After 24 h impregnation, the cloth was dried at roomtemperature first in the air for 2 days and then in vacuo for another 2days. Preparation for 1-acrylic and 1-nylon fibers: the nylon andacrylic fibers were washed in boiling 2-propanol for 4 h and then driedin vacuo at 323 K before use. Representative 2 g samples were thenimmersed in various aqueous solutions of 1 at 353 K for 2 h and then atroom temperature for 1 day. Most of the water or excess solution wasremoved using a rotary evaporator or by filtration at room temperature.The 1-nylon or 1-acrylic samples were then dried at room temperaturefirst in the air overnight and then in vacuo for 2 days. The percentagesof 1 on the cloth or fibers were determined by both weight differenceand elemental analysis (by E+R Microanalytical Laboratory, Inc.).

[0077] Preparation of POM-Filter Paper. A 0.6-g sample of paper wasimmersed in various aqueous solutions of 1, 2, and 3 at room temperaturefor a few hours until the POM-paper sample appeared dry by visualinspection. The resulting POM-paper sample was then dried in vacuo atroom temperature overnight. In a control experiment, the unmodifiedpaper was also treated with water and dried under identical conditions.

[0078] Comparison of Fabrics Unmodified or Modified with 1 in theAerobic Oxidation of CH₃CHO and CH₃SH. In all reactions, 0.5 g of1-modified or unmodified cloth or fiber was hung in a 250-mLround-bottom flask covered with aluminum foil and sealed with a septumstopper. This apparatus was taken through three degas/gas cycles withAr, evacuated and then purged with O₂. Next, 25 μl of gaseous CH₃CHO (or50 μl CH₃SH) and 25 μl C₂H₆ (internal standard) were added to the flaskto start the reaction. The reactions were stirred using a digitalstirrer at 1200 rpm and maintained at room temperature under 1 atm ofO₂. For the oxidation of CH₃SH, reactions were carried out in threesteps. After 20 h of the above reaction or no detectable CH₃SH remainingin gas phase (the first step), an additional 500 μl CH₃SH was then addedto the apparatus to continue the reaction in the second step. Anadditional 500 μl CH₃SH was added to the apparatus to initiate thereaction in the third step after 20 hr reaction of the second step. Inall reactions, gaseous aliquots (1-mL) were extracted at various timesand analyzed by GC. Blank control reactions with the materials (modifiedor unmodified) absent from the otherwise identical reaction systems wererun at the same time. All reactions were run in duplicate to assessreproducibility and the averages reported.

[0079] Comparison of Paper Unmodified and Modified with 1 in the AerobicOxidation of CH₃SH and CH₃CHO. In all reactions, 0.1 g of 1-paper orunmodified filter paper was hung in a 250-mL round-bottom flask coveredwith aluminum foil and sealed with a septum stopper. This apparatus wastaken through three degas/gas cycles with Ar, evacuated and then purgedwith O₂. Next, 0.75 mL of gaseous C₂H₆ (internal standard) and 1.5 mL ofgaseous CH₃SH were added to the flask to initiate the CH₃SH reaction.Alternatively, 0.025 mL of gaseous C₂H₆ (internal standard) and 0.025 mLof gaseous CH₃CHO were injected into the flask to initiate the CH₃CHOreaction. The reactions were stirred at 1,200 rpm using a digitalstirrer and maintained at ambient temperature under 1 atm of O₂ for 3hrs. During the reaction, gaseous 1-mL aliquots were removed at varioustimes and analyzed by GC to determine the concentration of remainingCH₃SH or CH₃CHO in the gas phase. All reactions were run in duplicate toassess reproducibility and the averages reported.

[0080] Evaluation of Reusability of 1-Modified Fabrics in the AerobicOxidation of CH₃CHO. The reactions were run as described above. The1-fabrics were recovered by treating the fabrics in vacuo at roomtemperature for 2 days. The reactions involving these materials werethen run again under the conditions identical to those in the first run.

[0081] Comparison of Fabrics Unmodified or Modified with 1 in theRemoval of NH₃. In all reactions, 0.5 g of modified or unmodified clothor fiber was hung in a 5-L round-bottom flask sealed with a septumstopper. This apparatus was taken through three degas/gas cycles withAr. Next, 1-mL of gaseous NH₃ was injected into the flask to start thereaction. The reactions were stirred using a digital stirrer at 500 rpmand maintained at room temperature under 1 atm of Ar. After 1 hrreaction, 100-mL gaseous aliquots were extracted by the detector tube toanalyze the concentration of the remaining NH₃. All reactions were runin duplicate.

[0082] Evaluation of Fabrics Unmodified or Modified with 1 in theDeodorization of a Simulated Polluted Atmosphere (CH₃CHO₃CH₃SH, andNH₃). The reaction apparatus was prepared following almost the sameprocedure as described above, except that 500-mL flask was used. C₂H₆(50μl), CH₃CHO(50 μl), CH₃SH(500 μl) and NH₃ (500 μl) were injectedsimultaneously into the apparatus to start the reaction. The reactionswere stirred using a digital stirrer at 1,200 rpm and maintained at roomtemperature under 1 atm of O₂. All reactions were run in duplicate toassess reproducibility and the averages reported.

[0083] Evaluation of Paper and POM-Paper with a Simulated PollutedAtmosphere. The reaction apparatus was prepared following the sameprocedure described above, except that a 500-mL flask was used. Thegases C₂H₆(1 mL), CH₃CHO(0.5 mL), CH₃SH(2 mL) and NH₃(0.5 mL) wereinjected simultaneously into the apparatus to start the reaction. Theflask contents were stirred using a digital stirrer at 1,200 rpm andmaintained at room temperature under 1 atm of O₂. After the reaction,gaseous 1-mL aliquots were removed and analyzed by GC to determine theconcentration of remaining CH₃CHO and CH₃SH in the gas phase. Theconcentration of remaining NH₃ was checked by Sensidyne®/Gastec detectortube.

[0084] Characterization. The DRIFT spectra of H₅PV₂Mo₁₀O₄₀ (1) modifiedSmoklin®, cotton cloth, acrylic fiber and nylon fiber are all similar tothat of the unsupported H₅PV₂Mo₁₀O₄₀ powder in the typical IR range(600-1200 cm⁻¹) for polyoxometalates, indicating that 1 is present onthe surface of all the modified fabrics (see FIG. 1, 5 wt % 1-acrylicfiber). The SEM pictures in FIG. 2 demonstrate that clusters of 1 areformed unevenly on the surface of the fabrics during the preparation of1-acrylic. The size of most clusters of 1 on 1-Smoklin® (5 wt %) and1-acrylic (5 wt %) are in the 1-5 μm range.

[0085] Gas Phase Reactions. In all gas phase reactions, the overallobserved consumption of the reagents reflects both the reactions of thereagents and their adsorption of the glass and cloth surfaces.

Example 1

[0086] Comparison of Catalytic Efficiencies of the 1-Fabrics in theAerobic of Oxidation CH₃CHO. All gas phase reactions were run at roomtemperature and under 1 atm O₂ pressure. FIG. 3 displays the consumption(concentration versus time) curves when no catalyst, Smoklin® alone and1-Smoklin® (with both 5 wt % and 40 wt % of 1) were used under otherwiseidentical reaction conditions. A comparison of the curves for theSmoklin® alone and the catalyst-free control experiment indicates thatthe Smoklin® has no significant activity. For the Smoklin® modified by1, significant activity is observed even when the weight percentage of 1is as low as 5 wt %. Additionally, FIG. 3 reveals that 1-Smoklin®removes a contaminant from the gas phase at a much higher rate thanunmodified Smoklin®, which is another advantage of the presentinvention.

[0087] Table 1 summarizes the results for different cloth and fibersystems in 3 hr reactions. All the unmodified fabrics, the 1-nylon (evenwhen the present of 1 is as high as 15 wt %) and the 1-cotton cloth (5wt % of 1) exhibit little or no activity. In contrast, significantactivity is demonstrated for the 1-Smoklin® (5 wt % of 1), the 1-acrylicfiber (5 wt % of 1) and the 1-cotton cloth (15 wt % of 1) with nodetectable CH₃COOH present in gas phase. TABLE 1 Removal of CH₃CHO fromthe Gas Phase by Polyoxometalate-Modified Fabrics.^(a) Consumption ofFabric CH₃CHO (%)^(b) None^(c) 9 Smoklin ® 15 1-Smoklin ® (5 wt % 1) 491-Smoklin ® (10 wt % 1) 55 1-Smoklin ® (40 wt % 1) 89 acrylic 131-acrylic (5 wt % 1) 62 cotton 26 1-cotton (5 wt % 1) 30 1-cotton (15 wt% 1) 56 nylon 19 1-nylon (15 wt % 1) 22

Example 2

[0088] Evaluation of Reusability of the 1-Fabrics in the AerobicOxidation of CH₃CHO. Table 2 illustrates that the reusability of1-Smoklin® (5 wt % and 40 wt %) and 1-acrylic (5 wt %) as catalysts inthe aerobic oxidation of CH₃CHO is very high. The catalytic activity of1-Smoklin® does not decrease significantly upon the recovery treatmentin vacuo and reuse. TABLE 2 Reusability of H₅PV₂Mo₁₀O₄₀ (1)-ModifiedFabrics in the Removal of CH₃CHO in the Gas Phase.^(a) Consumption % ofCH₃CHO^(b) Fabric first use second use^(c) third use^(d) 1-Smoklin ® (5wt %) 49 40 42 1-Smoklin ® 89 82 83 (40 wt %) 1-acrylic (5 wt %) 62 3032

Example 3

[0089] Comparison of Catalytic Activities of the 1-Fabrics in theAerobic Oxidation of CH₃SH. Table 3 summarizes the catalytic activitiesof different polyoxometalate-modified fabrics of the present inventionin the oxidation of CH₃SH. All of the unmodified fabrics and 1-cottoncloth (5 wt %) exhibit little or no activity, while 1-Smoklin® (5 wt %),1-acrylic (5 wt %) and 1cotton cloth (15 wt %) all possess significantactivities. Not wishing to be bound by theory, the high activitiesobserved for the anaerobic reactions involving 1-Smoklin® (5 wt %) and1-acrylic (5 wt %) indicate that 1 most likely functions as a redoxcatalyst, not simply as a radical chain initiator in the aerobicreactions. The reversible redox chemistry of 1 accounts for the betteractivity observed in the presence of O₂. In all the reactions containing1, dimethyl disulfide (CH₃SSCH₃) is present as the predominant productin gas phase, while in the blank and control reactions, no detectableproduct exists. TABLE 3 Removal of CH₃SH in the Gas Phase by 1-ModifiedFabrics.^(a) Consumption % of CH₃SH^(b) Step 1 Step 2 Step 3 200 ppm^(c)2000 ppm^(d) 2000 ppm^(e) Fabric at 3 hr at 2 hr at 2 hr Blank (O₂)^(f)36 11 — Smoklin ® (O₂) 30 12 — 1-Smoklin ® (5 wt %, Ar) 100 85 141-Smoklin ® (5 wt %, O₂) 100 96 47 acrylic (O₂) 27  9 — 1-acrylic (5 wt%, Ar) 100 79 11 1-acrylic (5 wt %, O₂) 100 100  100  Cotton (O₂) 33 11— 1-Cotton (5 wt %, O₂) 44 — — 1-Cotton (15 wt %, O₂) 100 52 13 (3 hr)

Example 4

[0090] Comparison of NH₃ Removal Capabilities of the 1-Fabrics. Theresults in Table 4 demonstrate that 1 modified Smoklin®, acrylic fiberand cotton cloth are much more active in deodorizing NH₃ than theuntreated fabrics. The mole ratios of 1 to NH₃ are 1:3.1 ant 1:1 for thereactions of the fabrics modified with 5 wt % and 15 wt % of 1,respectively. Not wishing to be bound by theory, the mechanism likelyinvolves the acid-base process in equation 1.

H₅PV₂Mo₁₀O₄₀ +xNH₃→H_(5-x)PV₂Mo₁₀O₄₀ ^(−x) +xNH₄ ⁺  (1)

[0091] TABLE 4 Removal of NH₃ in the Gas Phase by 1-ModifiedFabrics.^(a) Consumption % Fabric of NH₃ ^(b) Smoklin ® 23 1-Smoklin ®(5 wt %) 98 acrylic 30 1-acrylic (5 wt %) 97 cotton 36 1-cotton (5 wt %)69 1-cotton (15 wt %) 99

Example 5

[0092] Comparison of Overall Deodorizing Capabillties of the 1-Fabrics.The deodorizing efficiencies of 1-modified fabrics were furtherevaluated in the contaminated atmosphere simulated by the simultaneouspresence of CH₃CHO, CH₃SH and NH₃. The results in Table 5 indicate that1-modified Smoklin®, acrylic and cotton cloth are much more effectivethan the corresponding unmodified fabrics. TABLE 5 Simultaneous Removalof CH₃CHO, CH₃SH and NH₃ in the Gas Phase by 1-Modified Fabrics.^(a)Consumption %^(b) Fabric CH₃CHO CH₃SH NH₃ Smoklin ® 31 9 51 1-Smoklin ®(5 wt %) 84 68 100 acrylic 27 6 47 1-acrylic (5 wt %) 63 92 100 cotton33 10 78 1-cotton (15 wt %) 86 66 100

[0093] The collective data from the gas phase reactions indicate thatmodifying the cloth or fiber systems with 1 can improve their activityfor removing both oxidizable organic compounds by reaction with O₂, andbasic compounds by proton donation from the polyoxometalate.

Example 6

[0094] Comparison of Catalytic Efficiencies in the Aerobic of OxidationCH₃SH by 1-Paper. Prior to all reactions, both the unmodified paper andthe 1-paper were prepared using identical protocols, except that for theunmodified paper, only 1-free water was present in the immersion step.In Table 6, the catalytic activity of 1-paper is compared with theunmodified filter paper for the removal of CH₃SH. The results indicatethat the deposition of 1 on to the paper definitely increases thepaper's reactivity. The amount of 1 incorporated into the paper is animportant parameter for the reactivity. As for the 1-fabrics, dimethyldisulfide was the main detectable product in the 1-paper reactions,implying that the same mechanism was involved. A color change alsoaccompanied this redox reaction (the 1-paper turned from light orange todark green). The control reaction using the unmodified paper reactionproduced no detectable dimethyl disulfide or other products. TABLE 6 TheAerobic Oxidation of CH₃SH in gas phase catalyzed by 1-Paper.^(a) %Consumption of Sample CH₃SH^(b) Turnovers^(c) Paper 10 — 30 wt % 1-Paper16 0.6 37 wt % 1-Paper 45 1.4 45 wt % 1-paper 61 1.6

Example 7

[0095] Removal in the Gas Phase of CH₃CHO by 1-Paper. Table 7 summarizesdifferent efficiency of the unmodified and 1-modified paper in theremoval of CH₃CHO in gas phase. Better removing efficiency was observedfor the 1-paper than the untreated paper. As for the CH₃SH oxidationreaction, the amount of 1 deposited on the paper again influences thepaper's reactivity. TABLE 7 The Removal of CH₃CHO in gas phase by1-Paper.^(a) % Consumption Sample of CH₃CHO^(b) Paper 9 15 wt % 1-Paper12 30 wt % 1-Paper 23 45 wt % 1-paper 45 60 wt % 1-paper 63

Example 8

[0096] Comparison of Overall Deodorizing Capabilities of POM-Paper.Table 8 illustrates the reactive behavior of the POM-paper and POM-freepaper in the polluted air model (CH₃CHO, CH₃SH and NH₃ all present inthe atmosphere). The results indicate that 1-paper, 2-paper, and 3-paperare much more effective than the corresponding POM-free paper inremoving all the target gaseous molecules. More importantly, the dataindicate that the paper modified with different POM have differentselectivity, implying that the rates of different pollutant uptakeprocesses vary with the POM-paper. TABLE 8 Simultaneous Removal ofCH₃CHO, CH₃SH and NH₃ in the Gas Phase Catalyzed by POM-paper.^(a) %Consumption, Turnover^(b) CH₃CHO CH₃SH NH₃ paper 28, — 9, —  65, —1-paper (60 wt %) 87, 0.57 93, 2.4 100, — 2-paper (60 wt %) 94, 0.62 87,2.3 100, — 3-paper (60 wt %) 77, 0.51 96, 2.5 100, — # hung in the flaskcovered with aluminum foil and sealed with a septum stopper. All valuesare averages of two experiments.

[0097] Throughout this application, various publications are referenced.The disclosures of these publications in their entireties are herebyincorporated by reference into this application in order to more fullydescribe the state of the art to which this invention pertains.

[0098] It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present inventionwithout departing from the scope or spirit of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only.

What is claimed:
 1. A method for removing a contaminant from the gasphase, comprising contacting an article comprising a fabric and at leastone polyoxometalate, wherein the polyoxometalate is incorporated in thefabric to produce a polyoxometalate-modified fabric, with the gas phasecontaining the contaminant.
 2. The method of claim 1, wherein thepolyoxometalate has the formula[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o, and p is greater than or equal tofour; and the sum of k, m, and q is greater than zero, and A is acounterion.
 3. The method of claim 2, wherein M comprises a d-blockelement having at least one d-electron.
 4. The method of claim 2,wherein M comprises titanium, chromium, manganese, cobalt, iron, nickel,copper, rhodium, silver, palladium, platinum, mercury, or ruthenium. 5.The method of claim 2, wherein M comprises manganese.
 6. The method ofclaim 2, wherein M comprises cobalt.
 7. The method of claim 2, wherein Mcomprises ruthenium.
 8. The method of claim 2, wherein X comprisesphosphorus, silicon, aluminum, boron, cobalt, zinc, or iron.
 9. Themethod of claim 2, wherein A comprises a quatemary ammonium cation;proton; alkali metal cation; alkaline earth metal cation; ammoniumcation; d- or f-block metal complex, or a combination thereof.
 10. Themethod of claim 2, wherein A is silver.
 11. The method of claim 2,wherein A is gold.
 12. The method of claim 2, wherein s is from 19 to460.
 13. The method of claim 2, wherein the sum of k and q is greaterthan or equal to one, the sum of k, m, n, o, p, and q is 12, and s is40.
 14. The method of claim 2, wherein k is not zero.
 15. The method ofclaim 2, wherein q is not zero.
 16. The method of claim 1, Wherein thepolyoxometalate has the formula [X^(g+)V_(b)M^(h+)_(c)Z_(12-b-c)O₄₀]^(u−)[A], wherein X is at least one p-, d-, or f-blockelement; g+ is the charge of X; M is at least one f-block element ord-block element having at least one d-electron, wherein M is notvanadium; h+ is the charge of M; Z is tungsten, molybdenum, niobium, ora combination thereof; b is from 0 to 6; c is from 0 to 6, wherein thesum of b and c is greater than or equal to one; u is greater than 3; andA is a counterion.
 17. The method of claim 16, wherein thepolyoxometalate has the formula [X^(g+)V_(b)Z_(12-b)O₄₀]^(u−)[A],wherein X is at least one phosphorus, silicon, aluminum, boron, zinc,cobalt, or iron; b is from 1 to 6, and u is greater than
 3. 18. Themethod of claim 1, wherein the polyoxometalate has the structure[X^(g+)M^(h+) _(c)Z_(12-c)O₄₀]^(u−)[A], wherein X^(g+) is at least onephosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; c is from 1to 6, and u is greater than or equal to
 3. 19. The method of claim 1,wherein the polyoxometalate has the formula [X^(i+) ₂V_(u)M^(j+)_(v)Z_(18-u-v)O₆₂]^(w−)[A], wherein X is at least one p-, d-, or f-blockelement; i+ is the charge of X; M is at least one f-block element ord-block element having at least one d-electron, wherein M is notvanadium; j+ is the charge of M; Z is tungsten, molybdenum, niobium, ora combination thereof; u is from 0 to 9; v is from 0 to 9, wherein thesum of u and v is greater than or equal to one; w is greater than orequal to 4; and A is a counterion.
 20. The method of claim 19, whereinthe polyoxometalate has the formula [X^(i+) ₂V_(u)Z_(18-u)O₆₂]^(w−)[A],wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron,zinc, cobalt, or iron; u is from 1 to 9; and w is greater than or equalto
 4. 21. The method of claim 19, wherein the polyoxometalate has theformula [X^(i+) ₂M^(j+) _(v)Z_(18-v)O₆₂]^(w−)[A], wherein X is at leastone phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron;v is from 1 to 9; and w is greater than or equal to
 4. 22. The method ofclaim 1, wherein the polyoxometalate has the formula[YV_(x)Z_(12-x)O₄₀][A], wherein Y is phosphorus, silicon, or aluminum; Zis tungsten or molybdenum; x is from 1 to 6, and A is a counterion. 23.The method of claim 1, wherein the polyoxometalate further comprises anorganic group, an organosilyl group, an other p-block organometallicgroup, or a d-block organometallic group, wherein the organic group, theorganosilyl group, the other p-block organometallic group, or thed-block organometallic group is bonded to the polyoxometalate.
 24. Themethod of claim 1, wherein the polyoxometalate comprises H₅PV₂Mo₁₀O₄₀.25. The method of claim 1, wherein the polyoxoinetalate comprisesK₈Co₂W₁₁O₃₉.
 26. The method of claim 1, wherein the fabric is preparedfrom a fiber comprising polyamide, cotton, polyacrylic,polyacrylonitrile, polyester, polyvinylidine, polyolefin, polyurethane,polytetrafluoroethylene, or carbon cloth, or a combination thereof. 27.The method of claim 1, wherein the fabric is prepared from a fibercomprising cotton, polyacrylic, or polyacrylonitrile.
 28. The method ofclaim 1, wherein the article comprises a garment, drapery, carpet, orupholstery.
 29. The method of claim 1, wherein the polyoxometalate isfrom 2.5 to 60% by weight of the polyoxometalate-modified fabric. 30.The method of claim 1, wherein the polyoxometalate is H₅PV₂Mo₁₀O₄₀ andthe fabric is prepared from a polyacrylic fiber.
 31. The method of claim1, wherein the polyoxometalate is H₅PV₂Mo₁₀O₄₀ and the fabric isprepared from cotton.
 32. The method of claim 1, wherein the contaminantcomprises an aliphatic nitrogen compound, a sulfur containing compound,an aliphatic oxygenated compound, a halogenated compound, or acombination thereof.
 33. The method of claim 1, wherein the contaminantcomprises acetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide,methyl sulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine,styrene, propionic acid, n-butyric acid, n-valeric acid, iso-valericacid, or a combination thereof.
 34. The method of claim 1, wherein thecontaminant is removed from the gas phase at from −50° C. to 105° C. andat a pressure of from 0.1 to 30 atm.
 35. The method of claim 1, whereinthe contaminant is removed from the gas phase at from 25° C. to 105° C.and at 1 atm.
 36. The method of claim 1, wherein the contaminant isremoved from the gas phase at 25° C. and at 1 atm.
 37. A method forremoving a contaminant from the liquid phase, comprising contacting anarticle comprising a fabric and at least one polyoxometalate, whereinthe polyoxometalate is incorporated in the fabric to produce apolyoxometalate-modified fabric, with the liquid phase containing thecontaminant, with the proviso that when the fabric is carbon cloth, thenthe polyoxometalate is not H₅PV₂Mo₁₀O₄₀.
 38. A method for removing acontaminant from the gas phase or liquid phase, comprising contacting anarticle comprising a cellulosic fiber and at least one polyoxometalate,wherein the polyoxonietalate is incorporated in the cellulosic fiber toproduce a polyoxometalate-modified cellulosic fiber, with the gas phaseor liquid phase containing the contaminant.
 39. The method of claim 38,wherein the contaminant is in the gas phase.
 40. The method of claim 38,wherein the cellulosic fiber comprises wood or paper.
 41. The method ofclaim 38, wherein the cellulosic fiber comprises paper.
 42. Apolyoxometalate-modified fabric, comprising a fabric and at least onepolyoxometalate, wherein the polyoxometalate has the formula[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(t)O_(s)]^(y−)[A], wherein M is atleast one f-block element or d-block element having at least oned-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, ortantalum; X is at least one p-, d-, or f-block element, wherein X is notoxygen; k is from 0 to 30; m is from 0 to 160; n is from 0to 160; o isfrom 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; sis sufficiently large that y is greater than zero; and y is greater thanzero, wherein the sum of k, m, n, o, and p is greater than or equal tofour; and the sum of k, in, and q is greater than zero, and A is acounterion, wherein the polyoxometalate is incorporated in the fabric,with the proviso that when A is a proton, the polyoxometalate is not thereaction product between[V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(t)O_(s)]^(y−)[A] and apararosaniline compound, with the further proviso that thepolyoxometalate is not silicomolybdenic acid or its sodium salt,phosphomolybdenic acid, ammonium chromododecanemolybdenate, ammoniumsalt of hydrogen hexamolybdocobaltic acid, para-tungstic acid or itsammonium salt or sodium salt, meta-tungstic acid or its ammonium salt orsodium salt, phosphotungstic acid or its salt, silicotungstic acid orits salt, dodecane tungstodicobaltic acid or its salt,phosphotungstomolybdenic acid or its salt, or phosphovanadomolybdenicacid or its salt, with the further proviso that when the fabric iscarbon cloth, the polyoxometalate is not H₅PV₂Mo₁₀O₄₀.
 43. The fabric ofclaim 42, wherein k is greater than or equal to one.
 44. The fabric ofclaim 42, wherein the polyoxometalate further comprises an organicgroup, an organosilyl group, an other p-block organometallic group, or ad-block organometallic group, wherein the organic group, the organosilylgroup, the other p-block organometallic group, or the d-blockorganometallic group is bonded to the polyoxometalate.
 45. An articlecomprising the polyoxometalate-modified fabric of claim
 42. 46. Anarticle comprising the polyoxometalate-modified fabric of claim
 44. 47.The article of claim 45, wherein the article is garment, drapery,carpet, or upholstery.
 48. The article of claim 46, wherein the articleis garment, drapery, carpet, or upholstery.
 49. A method for making thepolyoxometalate-modified fabric of claim 42, comprising contacting thefabric with a polyoxometalate to produce the polyoxometalate-modifiedfabric.
 50. The method of claim 49, wherein the fabric is contacted witha mixture comprising the polyoxometalate and a solvent.
 51. The methodof claim 49, wherein the contacting step is conducted at from 0 to 100°C.
 52. The method of claim 50, wherein the solvent comprises water,acetone, toluene, or carbon dioxide.
 53. The method of claim 50, whereinthe solvent can be used in supercritical drying technology.
 54. Themethod of claim 49, further comprising drying thepolyoxometalate-modified fabric after the contacting step.
 55. Themethod of claim 54, wherein the drying step is from 0 to 220° C. at orbelow atmospheric pressure.
 56. The method of claim 54, wherein thedrying step is conducted under supercritical conditions.